US3356698A - Preparation of omega-hydroximinoalkanoic acids - Google Patents

Preparation of omega-hydroximinoalkanoic acids Download PDF

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US3356698A
US3356698A US316184A US31618463A US3356698A US 3356698 A US3356698 A US 3356698A US 316184 A US316184 A US 316184A US 31618463 A US31618463 A US 31618463A US 3356698 A US3356698 A US 3356698A
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acid
temperature
preparation
acids
mole
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Lafont Pierre
Thiers Michel
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Rhone Poulenc SA
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Rhone Poulenc SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/01—Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/03—Monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

  • the w-hydroximinoalkanoic acids are of value in the production of the corresponding w-aminoalkanoic acids, into which they may be converted by catalytic hydrogenation by known methods for compounds of this type, for example by hydrogenation in the presence of Raney metal under atmospheric or higher pressure, optionally in the presence of ammonia.
  • the w-aminoalkanoic acids are useful starting materials for the preparation of polyamides which may be employed for the preparation of films, fibres and moulded objects.
  • IZ-aminododecanoic acid is particularly valuable for this purpose.
  • IZ-aminododecanoic acid consists in hydrolysing dodecanolactam, which is itself prepared in two stages from cyclododecanone via the oxime of this ketone.
  • n is an integer from 3 to inclusive, and especially valuable for the preparation of l2-hydroximinododecanoic acid.
  • cycloalkanones having from 5 to 7 cyclic carbon atoms are converted into a,a-di(hydroximino)cycloalkanones when they are nitrosated either by a mixture of nitric oxide and air in the presence of catalytic quantities of hydrochloric acid (US. Patent No. 2,844,630), or by an alkylnitrite in concentrated hydrochloric acid medium (US. Patent No. 2,999,875). It is known also from the same U.S.
  • 12-hydroximinododecanoic acid which has a melting point of 112113 C.
  • 8-hyclroximinocaprylic acid which has a melting point of 1l1l 12 C.
  • w-aminoalkanoic acids are produced in excellent yield by a process requiring only two stages, the first stage being the production of an w-hydroximinoalkanoic acid by the process described above, and the second stage being a reduction of the w-hydroximinoalkanoic acid, thus obtained, for example by the known methods described above.
  • a solution of cycloaliphatic ketone of Formula II is prepared in an organic solvent which is inert under the reaction conditions, for example an aliphatic or alicyclic hydrocarbon, which may be substituted for example by one or more halogen atoms, such as hexane, heptane, cyclohexane, chloroform or carbon tetrachloride.
  • Concentrated sulphuric acid preferably of density 1.84 (66 Baum) is then gradually added in a quantity such that the ratio sulphuric acidzketone is between 1:1 and 5:1, preferably about 3:1.
  • acid of density 1.84 100% acid may be employed, but such acid does not afford any advantage either in the quality or the yield of the product.
  • nitrosating agents which may be employed include more especially nitrosyl sulphuric acid, nitrosyl halides (for example nitrosyl chloride), alkali metal salts of nitrous acid such as sodium nitrite or potassium nitrite, and nitrous vapours obtained, for example, by the action of sulphuric acid on an alkali nitrite or by oxidation of ammonia in air.
  • Nitrosyl sulphuric acid is particularly suitable. It can be introduced in crystalline form or in the form of a solution in sulphuric acid, for example in a proportion by weight of 50:50.
  • the sulphuric acid employed may be in anhydrous form or in the commercial -97% concentrated form.
  • the medium in which the reaction takes place is cooled and the temperature of this medium is maintained at a value which is preferably proportional to the size of the ring of the ketone starting material.
  • the temperature is preferably below 70 C.
  • the temperature should not be allowed to rise too far in an attempt to accelerate the reaction, and in practice there is no advantage in raising the temperature to more than 20 to 30 C. above the temperatures previously indicated during the mixing of the reactants.
  • the temperature should be below 70 C. during the period of contact, at a temperature of 20-25 C., a period of 2-3 hours is satisfactory, while at 40 C. a period not substantially greater than 1 hour should be employed, If the reactants are allowed to remain in contact for too long, there is a tendency for the corresponding amido acid, and in some cases tarry products, to form.
  • the reaction mass thus obtained is thereafter hydrolysed on ice, optionally after separation of the layer of organic solvent, whereafter the hydroximino acid formed is isolated by the application of any appropriate method, particular account being taken of the solubility of this amino acid.
  • hydrolysis gives an insoluble product, as in the case of 12-hydroximinod0decanoic acid, it is sufiicient to separate it by filtration, and to wash and optionally to recrystallise it.
  • the hydrolysis may result in an aqueous solution of the hydroximino acid, which is then isolated by extraction with the aid of an appropriate organic solvent.
  • these hydroximino acids are soluble in some ordinary organic solvents, such as acetones and ethanol, but sparingly soluble in methyl acetate and benzene.
  • cycloalkanone a mixture of cycloalkanone and cycloalkanol such as is obtained by oxidation of cycloalkanes by means of oxygen or by means of gaseous mixtures containing oxygen.
  • the hydrogenation in the presence of Raney nickel or cobalt may take place under atmospheric pressure or under pressures ranging up to 200 kg./cm. preferably about kg./cm. and at temperatures between 20 and 100 C. It is recommended that the operation be carried out in the presence of a concentrated, e.g., 20-35% aqueous ammonia solution, so as to block the acid function and thus to avoid polycondensation reactions between the NH and COOH groupings of the amino-acid formed.
  • a concentrated, e.g., 20-35% aqueous ammonia solution so as to block the acid function and thus to avoid polycondensation reactions between the NH and COOH groupings of the amino-acid formed.
  • hydrogenation may be carried out at ambient temperature, that is to say, at 1525 C., and under normal pressure or under a pressure in the neighbourhood thereof, with a small quantity of platinum, for example about 1% by weight in relation to the hydroximino-acid employed.
  • amido-acid of formula NH CO(CH -CO OH has already been described by Heyes and Robert, who obtained it by a different process, (see J. Chem. Soc. p. 4935 (1952)).
  • the autoclave was thereafter degassed and the reaction mass filtered. After evaporation in vacuo, the filtrate gave 0.4 g. of unreacted 12-hydroximinododecanoic acid.
  • the filter cake was taken up in 150 cc. of a 50/ 50 mixture of water and n-propanol at the boiling point. The mixture was hot-filtered, and the filtrate was then concentrated to a volume of 60 cc. There was thus obtained a crystalline mass which gave 2.5 g. of product melting at 179180 C. and had an amino-acid titre of about 95% (determined by titration of the amine function by perchloric acid). Taking into account the recovered hydroximino-acid, the amino-acid yield is about 65% of 100% pure product.
  • Example III The procedure of Example 11 is followed, starting with 9.8 g. of cyclohexanone, (0.1 mole) in solution in 40 cc. of hexane. During the running-in first of the sulphuric acid (10 minutes) and then of the nitrosylsulphuric acid (20 minutes), the temperature is maintained between 16 and 20 C. The mixture is thereafter maintained at 20 C. for about 1 hour, hydrolysed and treated as before. There are thus obtained 8.5 g. of crude product which, on recrystallisation from a mixture of methyl acetate and ether (50: 50), gives 5.53 g. of w-hydroximinocaproic acid, M.P. 114-116 C. (Yield 38.1%). On hydrogenation by the usual methods on Raney nickel (60 C., 100 atmospheres, excess of ammonia), 6-aminocaproic acid. M.P. 200 C is obtained.
  • Raney nickel 60 C., 100 atmospheres, excess of ammonia
  • EXAMPLE V Into a 100 cc. spherical flask are introduced 7.7 g. (0.05 mole) of cyclodecanone in solution in 20 cc. of cyclohexane. There are run-in drop-by-drop with stirring 9.2 cc. .(0.16 mole) of sulphuric acid (66 B.). At the end of 15 minutes, a solution of 6.1 g. (0.048 mole) of nitrosylsulfuric acid in 6.1 g. of sulphuric acid (66 B.) is slowly added, whereafter the reaction is allowed to continue for one hour, the temperature being maintained between 16 and 20 C. throughout the operation.
  • Process for the preparation of an w-hydroximinoalkanoic acid of formula HON:CH(CH COOH wherein R represents a divalent radical selected from the group consisting of polymethylene radicals containing 2 to 9 carbon atoms and polymethylene radicals containing 2 to 9 carbon atoms and having one lower alkyl substituent which comprises the steps of (1) contacting a ketone of formula with nitrosylsulphuric acid, a nitrosyl halide, an alkali metal salt of nitrous acid or nitrous vapours for less than 3 hours at up to 70 C. in the presence of concentrated sulphuric acid, (2) hydrolysing the product, and (3) separating the w-hydroximinoalkanoic acid produced.
  • step (1) which comprises the steps of (1) contacting a solution in an organic solvent of a cyclic ketone of formula of 1 to 5 moles of sulphuric acid per mole of said cyclic ketone, (2) hydrolysing the reaction mass resulting from step (1) and (3) separating the whydroximinoalkanoic acid thus produced.
  • Process for the preparation of l2-hydroximinododecanoic acid which comprises. contacting cyclododecanone in an inert solvent and in the presence of concentrated sulphuric acid with a substantially equimolecular amount of nitrosyl sulphuric acid, a nitrosyl halide, an alkali metal salt of nitrous acid, or nitrous vapours, using more than one mole of sulphuric acid per mole of cyclododecanone, for less than three hours at up to C., hydrolysing the product with water, and separating the 12-hydroximinododecanoic acid produced.
  • nitrosating agent is nitrosyl sulphuric acid.
  • Process for the preparation of l2-hydroximinododecanoic acid which comprises contacting cyclododecanone in an inert solvent and in the presence of concentrated sulphuric acid with nitrosyl sulphuric acid, using one mole of the nitrosyl sulphuric acid per mole of cyclododecanone and one to five moles of sulphuric acid per mole of cyclododecanone, for from a few minutes to three hours at 0 to 70 C., hydrolysing the product with water and separating the 12-hydroximinododecanoic acid produced.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US316184A 1962-11-19 1963-10-14 Preparation of omega-hydroximinoalkanoic acids Expired - Lifetime US3356698A (en)

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FR915860A FR1349281A (fr) 1962-11-19 1962-11-19 Préparation d'acides omega-aminoalcanoïques

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3857510A (en) * 1971-10-14 1974-12-31 Allied Chem Ketone cleavage and products therefrom
US4073804A (en) * 1976-05-04 1978-02-14 Boise Cascade Corporation Producing glycine by the reductive amination of glyoxylic acid
US10354765B2 (en) 2015-10-21 2019-07-16 Commissariat à l'énergie atomique et aux energies alternatives Use of hydroxyiminoalkanoic acids as anti-nitrous agents in operations of reductive stripping of plutonium

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3024276A (en) * 1956-11-16 1962-03-06 Montedison Spa Process for the preparation of aminoacids from organic peroxides and nitrogen oxide

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3024276A (en) * 1956-11-16 1962-03-06 Montedison Spa Process for the preparation of aminoacids from organic peroxides and nitrogen oxide

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3857510A (en) * 1971-10-14 1974-12-31 Allied Chem Ketone cleavage and products therefrom
US4073804A (en) * 1976-05-04 1978-02-14 Boise Cascade Corporation Producing glycine by the reductive amination of glyoxylic acid
US10354765B2 (en) 2015-10-21 2019-07-16 Commissariat à l'énergie atomique et aux energies alternatives Use of hydroxyiminoalkanoic acids as anti-nitrous agents in operations of reductive stripping of plutonium

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GB997177A (en) 1965-07-07
NL300643A (enrdf_load_stackoverflow)
FR1349281A (fr) 1964-01-17

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